Composition of halogen containing film forming material



Patented Feb. 17, 1942 COMPOSITION OF HALOGEN CONTAINING FILM FORMINGMATERIAL Kurt Desamari.

Leverkusen-I. G. Werk, and

Reinhard Hebermehl, Cologne-Deutz, Germany, assignors to I. G.Farbenindustrie Aktiengesellschaft, Frankfort-on-the-Main, Germany NoDrawing. Original application March 6, 1937, Serial No. 129,381. Dividedand this application May 4, 1940, Serial No. 333,368.

many March 7, 1936 Claims.

The present invention relates to new condensation products which may bedefined as acetals of hydroxyalkylarylethers, i. e. of compounds of thegeneral formula,

in which X stands for O or S. More particularly it relates to newcompositions of matter comprising said acetals and halogen containingfilm forming materials.

It has been found that acetals of the character described can be easilyprepared by causing alkali metal salts of aromatic hydroxy compounds,such as phenolates or naphtholates to react upon acetals of halogencontaining aliphatic alcohols. Another method consists in causingaldehydes to react upon hydroxyalkylarylethers. We have, furthermore,found that that these acetals if incorporated within halogen containingfihn forming materials exert remarkable properties chief among which isan enormous increase of elongation.

As hydroxyalkyl-arylethers there are preferably chosen those of thebenzene series such as those of phenol or cresols, though those of thenaphthalene series and of higher ring systems are not excluded from ourinvention.

As pointed out above the new condensation products are excellentsofteners for film forming materials, particularly for those containinghalogen. As examples of halogen containing film forming materials theremay be mentioned chlorinated rubber, polyvinylchloride, furthermore, theaddition products of hydro halic acids with caoutchouc, polymeric vinylesters of halogen containing acids such as polyvinylchloroacetate andfinally afterchlorination products of polyvinylchloride or of2-chlorobutadiene-1.3-po1ymerisates. In connection with these filmforming materials advantageously such softeners of the characterdescribed are employed as are liquid at ordinary temperature, either assuch or in admixture one with another. The outstanding efiect induced inthe said film forming materials by the incorporation of these softenersresults in a considerable increase of elongation. The said softenersare, furthermore, capable of effecting an increase of the brightness andof the adhesive capacity of the film forming materials to the base. Thenew softeners can, of course, be combined with other softeners or otheradditions, such as filling agents, pigments, resins and drying ornon-drying oils.

The characteristic softening effect of the com- In Gerpounds in questionis illustrated by the following tests:

Iron sheets are provided with a threefold varnish layer of the followingcomposition:

Parts by weight Chlorinated rubber 30 Softener 12 Titanium dioxide 21Xylene On drying, the sheets are allowed to age by a hour exposure toheat in a drying oven. The following table shows the behaviour of thevarnish layer on bending the sheet iron over a bar, the presence orabsence in the coating of cracks at a given diameter of curve beingtaken as an indication of the elasticity:

The above table shows that the new softeners are far superior to thehitherto known softeners such as chlorinated diphenyl and phthalic acidesters and also to the diaryldiethylethers which are closely relatedthereto from the chemical point of view.

The following examples illustrate the invention without restricting itthereto, the parts being by weight:

Example 1 An iron plate which has been well freed from rust is providedwith a varnish-layer of the following composition:

Parts Chlorinated rubber (65% chlorine content) 12 Formaldehyde acetalof cresoxyethanol- 3 Chlorinated diphenyl (57% chlorine content) 1.8 Redlead 60 A mixture of toluene-xylene (1:1) 23.2

On drying, there is applied twice a lacquer of the followingcomposition:

Parts Chlorigiated rubber (chlorine content 64%) 25 Formaldehyde acetalof phenoxyethanol 8 are dissolved in 52 parts of xylene or a mixture oftoluene-xylene (1:2) and intimately mixed with parts of iron oxide ortitanium dioxide.

A very adhesive, elastic, stable protecting layer is thus obtained.

Instead of chlorinated rubber there can be employed the products of theafterchlorination of polymerized 2-chloroor bromo-butadiene- 1.3 of achlorine content of 65%.

Example 2 Iron materials such as pipes, profiles, etc which are freefrom rust are provided with two or three coats of the following varnish:

Parts Afterchlorinated polyvinyl chloride (64% chlorine) 16 Formaldehydeacetal of the phenoxyethanol- 2 Formaldehyde acetal of thefi-hydroxy-ethylp-tolylsulfide 1 Acetaldehydeacetal of thephenoxyethanoL- 2 Red ferric oxide 10 Ethyl acetate 18 Butyl acetate 17Xylene 34 A well adherent, elastic coating is obtained which is stableagainst chemical influence.

Example 3 An elastic varnish of good adhesive properties which is stableagainst mineral oil is obtained when coating a sheet iron thrice withthe following batch:

Example 4 The varnish of the following composition is suited to protectiron articles towards chemical influence:

Parts Polyvinylchloride (56% chlorine) 10 Formaldehyde acetal ofphenoxyethanol 3 Red ferric oxide 5 Xylene 27 Butyl acetate 27Cyclohexanone 28 Example 5 A pine board is provided with two or threecoats of the following varnish:

Parts Chlorinated rubber (62% chlorine) Linseed oil (containing 1% ofcobalt-naphthenate) 12 Formaldehyde acetal of phenoxyethanol 4 Redferric oxide 15 Toluene 19 Xylene An elastic protecting layer is thusobtained which is weather-resistant.

In the following there are given some exsoda lye are evaporated todryness.

amples for the preparation of the acetals of hydroxyalkylarylethers madeuse of in the foregoing examples. In practice these acetals are preparedby heating the sodium salt of the aromatic hydroxy compound with anacetal of a halogen containing aliphatic alcohol in the absence of anydiluent. The resulting condensation product is isolated by distillationin vacuo.

Example 6 465 parts of sodium phenolate and 346 parts of formaldehyde-d1(B-chloroethyl) -acetal are stirred at 180 C. for 4 hours.

The reaction mixture is stirred with 2000 parts of Water and thendistilled in vacuo. The formaldehyde-di (fl-phenoxethyD-acetal thusobtained is a colorless oil which boils at 195-196 C. under 0.6 mm.pressure. It solidifies at 18 C.

Example 7 332 parts of acetaldehyde-di (p-chloroethyD- acetal arestirred at 200 C. with 412 parts of sodium phenolate for 5 hours.Thereupon the reaction mixture is stirred with 2000 parts of water whilethe oil is separated and distilled oil. The acetaldehyde-di(p-phenoxethyD-acetal boils at 188-190" C. under 0.6 mm. pressure.

Example 8 432 parts of o-cresol and 432 parts of 37% soda lye areevaporated to dryness in vacuo. The dry residue is heated with 380 partsof formaldehydedi (fl-chloroethyD-acetal at -205 C. for 5 hours. Bystirring with 2000 parts of water the precipitated sodium chloride isdissolved; hereafter the oil is separated from water and distilled invacuo. The formaldehyde-d1 (p-ocresoxethyl) -aceta1 is colorless oilwhich boils at 190 C. under 4 mm. pressure. It solidifies at 22 C.

Example 9 504 parts of p-thiocresol and 435 parts of 37% The residue isheated with 346 parts of formaldehyde-di (,8- chloroethyl)-acetal at-190 C. for 5 hours. After the reaction mixture has been stirred with2000 parts of water the oil is separated and distilled. Theformaldehyde-di (B-thiocresoxyethyl) acetal boils at 220-221 C. under0.6 mm. pressure. It solidifies at 37.5 C.

This application is a division of Serial No. 129,381, filed March 6,1937.

It will be understood that the details and examples hereinbefore setforth are illustrative only, and that the invention as broadly describedand claimed is in no way limited thereby.

What we claim and desire to protect by Letters Patent is:

l. A composition of matter comprising a halogen containing film-formingplastic material selected from the group comprising chlorinated rubber,polyvinyl chloride, and chlorobutadiene, and an acetal of a compound ofthe type formula aryl-X-alkyl-OH wherein X stands for a member of thegroup consisting of O and S as a plasticizer therefor.

2. A composition of matter comprising a halogen containing film-formingplastic material selected from the group comprising chlorinated rubber,polyvinyl chloride, and chlorobutadiene, and an acetal of a compound ofthe type formula aryl-X-alkyl-OH wherein the X stands for a memberof'the group consisting of O and S and wherein the aryl group is aphenyl group as a plasticizer therefor.

3. A composition of matter comprising a halogen containing film-formingplastic material selected from the group comprising chlorinated rubber,polyvinyl chloride, and chlorobutadiene, and the formaldehyde acetal ofphenoxyethanol as a plasticizer therefor.

4. A composition of matter comprising a halogen containing film-formingplastic material selected from the group comprising chlorinated rubber,polyvinyl chloride, and chlorobutadiene, and the formaldehyde acetal ofcresoxyethanol as a plasticizer therefor.

5. A liquid coating composition comprising chlorinated rubber, an acetalof a compound having the type formula aryl X-alkyl-OH wherein X standsfor a member of the group consisting of O and S, and a volatile solvent.

6. A liquid coating composition comprising chlorinated rubber, an acetalof a compound having the type formula aryl-X-alkyl-OH wherein X standsfor a member of the group consisting of O and S, in which the aryl groupis a phenyl group, and a volatile solvent.

'7. A liquid coating composition comprising chlorinated rubber, anacetal of phenoxyethanol and a volatile solvent.

8. A liquid coating composition comprising chlorinated rubber, an acetalof cresoxyethanol and a volatile solvent.

LACilahiro.

9. A liquid coating composition comprising chlorinated rubber, aformaldehyde acetal of a compound having the type formulaaryl-X-alkyl'OH wherein X stands for a member of the group consisting ofO and S, and a volatile solvent.

10. A liquid coating composition comprising chlorinated rubber, theformaldehyde acetal of phenoxyethanol, and a volatile solvent.

11. A liquid coating composition comprising chlorinated rubber, the'formaldehyde acetal of cresoxyethanol, and a volatile solvent.

12. A composition of matter comprising chlorinated rubber and an acetalof a compound of the type formula aryl.X.alkyl.OH wherein X stands for amember of the group consisting of O and S as a plasticizer therefor.

13. A composition of matter comprising a chlorinated rubber and as aplasticizer therefor, an acetal of a compound of the type formulaaryl.X.alkyl.OH wherein X stands for a compound of the group consistingof O and S and wherein the aryl group is a phenyl group.

14. A composition of matter comprising chlorinated rubber and aformaldehyde acetal of phenoxyethanol as a plasticizer therefor.

15. A composition of matter comprising chlorinated rubber and theformaldehyde acetal of cresoxyethanol as a plasticizer therefor.

KURT DESAMARI. REINHARD HEBERMEHL.

